CN1166576C - Scale and/or corrosion inhibiting composition - Google Patents
Scale and/or corrosion inhibiting composition Download PDFInfo
- Publication number
- CN1166576C CN1166576C CNB008032459A CN00803245A CN1166576C CN 1166576 C CN1166576 C CN 1166576C CN B008032459 A CNB008032459 A CN B008032459A CN 00803245 A CN00803245 A CN 00803245A CN 1166576 C CN1166576 C CN 1166576C
- Authority
- CN
- China
- Prior art keywords
- composition
- acid
- aspartic acid
- poly aspartic
- oligopolymer
- Prior art date
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- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 238000005260 corrosion Methods 0.000 title claims abstract description 25
- 230000007797 corrosion Effects 0.000 title claims abstract description 25
- 230000002401 inhibitory effect Effects 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 24
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims description 14
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical group CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 4
- 238000005227 gel permeation chromatography Methods 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- 239000012964 benzotriazole Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011575 calcium Substances 0.000 abstract description 12
- 229910052791 calcium Inorganic materials 0.000 abstract description 12
- 239000003112 inhibitor Substances 0.000 abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002455 scale inhibitor Substances 0.000 abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052794 bromium Inorganic materials 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 229920002125 Sokalan® Polymers 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 230000005764 inhibitory process Effects 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ZNFNDZCXTPWRLQ-UHFFFAOYSA-N butane-1,1,1-tricarboxylic acid Chemical compound CCCC(C(O)=O)(C(O)=O)C(O)=O ZNFNDZCXTPWRLQ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- -1 methylene phosphonic acids Chemical class 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical group [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 235000016936 Dendrocalamus strictus Nutrition 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 101150033824 PAA1 gene Proteins 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229940096405 magnesium cation Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Physical Vapour Deposition (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Flanged Joints, Insulating Joints, And Other Joints (AREA)
- Lift Valve (AREA)
- Glass Compositions (AREA)
- Protection Of Pipes Against Damage, Friction, And Corrosion (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Plant Substances (AREA)
- Detergent Compositions (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
This invention relates to scale and/or corrosion inhibiting compositions for aqueous systems comprising (a) polyaspartic acid, and (b) a water soluble phosphonated oligomer. The compositions are effective scale inhibitors and corrosion inhibitors, but are also advantageous from an environmental standpoint because they are non-toxic, contain no heavy metals, and have little phosphorus. They also have significant calcium/hardness tolerance and are chlorine/bromine stable.
Description
Technical field
The present invention relates to a kind of inhibition fouling and/or corrosion compositions that is used for aqueous systems, it comprises: (a) poly aspartic acid and (b) water-soluble phosphoric acid salinization oligopolymer.Said composition is effective scale inhibitor and corrosion inhibitor, and sees it also is favourable from the viewpoint of environment, because they are atoxic, do not contain heavy metal and contains a spot of phosphorus.They also have tangible calcium/hardness tolerance and are that chlorine/bromine is stable.
Background technology
The water that is used in industry cooling or mining system is taken from rivers, lake, pond or groundwater reservoir.This kind water comprises the dissolved inorganic salt.When these water in cooling system by heat exchanger and cooling tower circulation time since vaporization losses a part of water.This has increased the concentration of inorganic salt in system.If surpass the solubleness of these salt in water, will precipitate.
Be deposited in along with salt on the internal surface of cooling system, they form fouling or settling.Fouling has suppressed effective heat to be shifted, and has limited flowing of water, and has promoted to form the corrosion under the settled layer.As a result, must remove fouling by cleaning.This cleaning is expensive, because necessary closing device produces labour cost, and delayed production.Consider these problems, prevent from that incrustation scale from forming preferably to remove fouling.
Fouling can be under an embargo to water treatment system by adding chelating or complex compound.Required chelating/complex compound is based on the stoichiometry of calcium and magnesium cation content in the aqueous systems that is cleaned.This method that suppresses fouling is expensive and does not use usually.
Before more than 50 year, find that some compound is as extremely effective scale inhibitor.This kind compound is to use and be referred to as " threshold values inhibitor " with the significantly lower amount of stoichiometry.The example of threshold values inhibitor is phosphonate and water-soluble acrylic/toxilic acid/sulfonic acid polymer or multipolymer.Corrosion inhibitor for example phosphonate, inorganic phosphate, pyrroles, zinc and molybdate often is to use with scale inhibitor.
Except effective usefulness, Water Treatment Chemicals must be acceptable on the environment.Environmental legislation bans use of the corrosion inhibitor that resembles chromic salt and so on, and general limitation is used all heavy metals now.Other trend is, Water Treatment Chemicals is atoxic, has a small amount of or do not have phosphorus, has high calcium/hardness tolerance, and stable to chlorine/bromine, and has high fouling and corrosion efficient simultaneously.Because these requirements, the Cost Growth of water causes higher utilization again/higher refrigeration cycle, and this has caused the water coolant of high hardness and alkaline matter content.
US5,523,023 relate to a kind of poly aspartic acid and tricarboxylic composition of phosphinylidyne butane of comprising, and it is as alkaline cleaner.US5,386,038 disclose the phosphatization oligopolymer with following general formula:
H[CHRCHR]
n-PO
3M
2
Wherein, at least one R base is COOM in each unit, CH
2OH, sulfonic group or phosphono, and another R base can be identical or different with first R group, is hydrogen or COOM, hydroxyl, phosphono, sulfonic group, sulfate, C
1-7Alkyl, C
1-7Alkenyl or carboxylicesters, the C that phosphono, sulfonic group, sulfate and/or hydroxyl replace
1-7Alkyl or C
1-7Alkenyl, and each M be positively charged ion so that the phosphatization oligopolymer is water miscible, and n is 1-6.These compositions have suppressed fouling and/or have been exposed to the corrosion of metal of aqueous systems.
Summary of the invention
The present invention relates to a kind of be used to suppress aqueous systems for example water coolant, the water and have high rigidity and the fouling and/or the corrosion compositions of the GEOTHERMAL WATER of alkalescence of digging up mine, its water-soluble phosphoric acid salinization oligopolymer that comprises significant quantity (a) poly aspartic acid and (b) have a following general formula forms to suppress fouling:
H[CHRCHR]
n-PO
3M
2
Wherein, at least one R base is COOM in each unit, CH
2OH, sulfonic group or phosphono, and another R base can be identical or different with first R group, is hydrogen or COOM, hydroxyl, phosphono, sulfonic group, sulfate, C
1-7Alkyl, C
1-7Alkenyl or carboxylicesters, the C that phosphono, sulfonic group, sulfate and/or hydroxyl replace
1-7Alkyl or C
1-7Alkenyl, and each M be positively charged ion so that the phosphatization oligopolymer is water miscible, and n is 1-6, usually greater than 1 with less than 6.
Composition is a synergistic action effect, because they are than the fouling of expecting of inhibition to a greater degree with regard to the fouling inhibition of single component is active.Said composition is qualified on the environment, because they are atoxic, does not contain heavy metal, and contains and contain phosphorus on a small quantity or not.They have tangible calcium/hardness tolerance, and are stable to chlorine/bromine, and have suppressed corrosion effectively.
Embodiment
The component of scale inhibitor composition (a) is the water-soluble poly aspartic acid.For the purposes of this invention, term " poly aspartic acid " should be intended to comprise the salt and the derivative of poly aspartic acid.The derivative of poly aspartic acid and salt thereof and poly aspartic acid be know and at US5, introduction is arranged in 523,023, it is hereby incorporated by.The preferred use is that the molecular weight of gel osmoticing chromatogram analysis method is 500-10000, preferably 1000-5000, the most preferably poly aspartic acid of 2000-4000.Poly aspartic acid preferably with the form of salt, particularly uses with the form of sodium salt or sylvite.Whether poly aspartic acid uses the pH that depends on handled aqueous systems with the form of acid or salt.The salt of poly aspartic acid is sodium salt preferably.The derivative that also can use poly aspartic acid is the acid anhydrides of poly aspartic acid for example, its under working conditions because hydrolysis can be transformed into poly aspartic acid.
The component of scale inhibitor composition (b) is a water-soluble phosphine carboxylic acyl oligopolymer salt, and particular certain cancers finds it is the mixture of oligopolymer usually.These oligopolymer are to be described in US5, and in 386,038, its content is drawn at this and is reference.The general structure of these water-soluble phosphine carboxylic acyl oligopolymer is:
H[CHRCHR]
n-PO
3M
2
Wherein, at least one R base is COOM in each unit, CH
2OH, sulfonic group or phosphono, and another R base can be identical or different with first R group, is hydrogen or COOM, hydroxyl, phosphono, sulfonic group, sulfate, C
1-7The alkane alkyl, C
1-7Alkenyl or carboxylicesters, phosphono, sulfonic group, sulfate, and/or the C of hydroxyl replacement
1-7Alkane alkyl or C
1-7Alkenyl, and each M be positively charged ion so that the phosphatization oligopolymer is water miscible, and n is 1-6, usually greater than 1 with less than 6.
The preferred water-soluble phosphine carboxylic acyl oligopolymer salt that uses is the following specific class salt with said structure general formula:
H[CH (CO
2Na)-CH (CO
2Na)]
nPO
3Na
2Wherein n is 1 to 5.
The weight ratio of phosphatization oligopolymer and poly aspartic acid is 8: 1 to 1: 12, preferred 4: 1 to 1: 9, and more preferably 1: 4 to 1: 9.
For some application; the preferred water solubility copolymer that adds is to the fouling composite inhibiting; phosphono-carboxylic acids polymkeric substance for example; toxilic acid or maleic anhydride polymkeric substance; acrylate copolymer; the multipolymer of methacrylate polymer and they and sulfonic acid functional group and/or phosphono functional group, preferably vinylformic acid/sulfonic acid copolymer or vinylformic acid/maleic acid.
Other selectable component comprises the phosphinylidyne butane tricarboxylic acid, tolyl-triazole, orthophosphoric acid salt, polyphosphate, hydroxy ethylene diphosphonic acid, amino three (methylene phosphonic acids).
The fouling composite inhibiting has suppressed the formation of lime carbonate, calcium phosphate, calcium sulfate and other scale forming matter.They particularly are used within the pH value scope of 8.0-9.0 and temperature is 40-65 ℃.The fouling composite inhibiting is to use with the minimum dose of 0.1ppm, but 5.0-500.0ppm preferably most preferably is 10.0-200.0ppm.
Shortenings
Following is the shortenings of using in an embodiment:
AA:AAMPS ACUMER 2000 vinylformic acid/sulfonic acid copolymer are by Rohm ﹠amp; Haas Co
Produce.
Vinylformic acid/sulfonic acid copolymer that AR-540 is produced by Alco Chemical Inc.
BTC phosphinylidyne butane tricarboxylic acid is also referred to as the Am into Bayhibit, by Bayer Co.
Produce.
MPY corrosion rate unit: millimeter/year.
The PAA poly aspartic acid is referred to as VPOC 2401, is produced by Bayer Co..
The water mixture of PCM phosphono-carboxylic acids oligopolymer salt is referred to as BRICORR
288, by Albright ﹠amp; Wilson Inc produces
The following example will illustrate specific embodiments of the present invention.They are not considered to limit application of the present invention.It should be noted that other embodiment also is utilizable.
Embodiment 1 (inhibition of calcium carbonate scaling threshold values)
With standard lime carbonate wobbler test the fouling inhibition of the blend of several inhibition foulings of containing PCM and PAA is assessed.Several contrasts have also been assessed.
Step comprises: add scale inhibitor composition sample (by the consumption shown in Table I and the II) to a solution that places 125 milliliters of wobbler flasks, this solution comprises 90.0 milliliters of DI water, 5.0 milliliters of calcium strong solution (14.7 gram CaCl
2.2H
2The O/ liter) and 5.0 milliliters of alkaline strong solutions ((1.59 gram Na
2CO
3+ 14.8 gram NaHCO
3)/liter).The water parameter of the initial testing of gained is: as CaCO
3Calcium=500ppm, as CaCO
3Total alkalescence=500ppm and PH=8.5).Then flask is covered and it was placed 16-18 hour in 50 ℃ on wobbler.After the time of shaking, whole sample solution is passed through Whatman #5 filter paper filtering.With filtrate then with the titration of 0.01MEDTA solution to determine to be retained in the content of the calcium in the test soln.The result is shown in Table I and the Table II, wherein each suppress per-cent be the mean value of 5 revision tests and wherein the inhibiting per-cent of calcium be by following calculating:
% threshold values restraining effect (%TI)=[(ppm A-ppmB) ÷ (500-ppmB)] * 100
Wherein:
The initial calcium concn of 500=500ppm lime carbonate
After the ppm A=test, in filtrate as CaCO
3The calcium concn of ppm; With
After the ppm B=test, in blank solution as CaCO
3The calcium concn of ppm.
The %TI of Table I PCM/PAA blend
| PCM ppm solid content | PAA ppm solid content | PCM: PAA ratio | ％TI |
| 25.0 | 0.0 | 25∶0 | 54.1±7.5 |
| 20.0 | 5.0 | 4∶1 | 56.4±6.5 |
| 12.5 | 12.5 | 1∶1 | 56.8±4.9 |
| 5.0 | 20.0 | 1∶4 | 60.0±6.0 |
| 3.1 | 21.9 | 1∶7 | 70.6±3.1 |
| 2.5 | 22.5 | 1∶9 | 57.4±4.0 |
| 0.0 | 25.0 | 0∶25 | 12.0±1.7 |
Result in table 1 has shown the threshold values restraining effect per-cent of PCM/PAA blend.For 4: 1 to 1: 9 solids ratios, the PCM/PAA blend of 1: 4 to 1: 9 ppm solids ratio particularly, synergetic property is to show significantly.
Table II shows result and the additional test result of selecting from Table I.Set test result to determine whether the PCM/PAA multipolymer shows synergetic property.
The synergistic effect of Table II blend
| Has only PCM | Has only PAA | 1: 7 32.1 70.6+38.5 2.5+22.5 of 1: 4 51.9 60.0+8.1 3.1+21.9 of the difference amplification ppm+ppm %TI %TI %TI 5+20 of the reality of PCM/PAA blend PCM+PAA ratio prediction 1: 9 20.4 57.4+37.0 |
| ppm ％TI | ppm ％TI | |
| 5.0 39.0 | 20.0 12.9 | |
| 3.1 21.0 | 21.9 11.1 | |
| 2.5 8.5 | 22.5 11.9 |
Data in the Table II show that PCM and PAA multipolymer reach the obvious higher %TI value (actual value) than theoretical prediction.Difference between actual value and the predictor is 8.1% to 38.5%.
Embodiment 2 rotors are bathed the corrosion test method
Soft steel (C1010) sample tube is tested as corrosion inhibitor with described composition.Use " rotor bath corrosion test " evaluation group compound.Step comprises: add in the corrosion inhibitor composition (consumption shown in the Table III) the surveyed a kind of solution to the sample cylinder, this solution comprises 7.8 liters of softening waters, 100.0 milliliters of rigid strong solutions (every liter 70.6 gram CaCl
2.2H
2O adds 42.0 gram MgCl
2.6H
2O), and 100.0 milliliters of strong solutions (whenever be upgraded to 8.5 gram Na
2CO
3+ 20.2 gram NaHCO
3+ 35.5 gram Na
2SO
4).The pH value of water is adjusted to 8.5.The soft steel sample tube is suspended from the water in the test jar by mandrel, and mandrel is attached on the driving gear again.Heating also makes water temperature remain on 50 ℃.Driving gear is opened with its standard speed.After 4 all day, close system, remove sample tube, clean and calculate the erosion rate of representing with MPY.With the results are shown in the Table III of the mean value of twice revision test.The result of this corrosion test is shown in down in the Table III.
The Table III rotor is bathed the result of corrosion test
| PCM, the ppm solid content | PAA, the ppm solid content | MPY |
| 25.0 | 0.0 | 20.1 |
| 20.0 | 5.0 | 9.8 |
| 15.0 | 10.0 | 6.5 |
| 10.0 | 15.0 | 6.1 |
| 5.0 | 20.0 | 10.8 |
| 0.0 | 25.0 | NA 1 |
When independent use, known PAA is extremely weak and is insufficient corrosion inhibitor.This test-results has confirmed this point.This test-results shows that also PCM is weak and is insufficient corrosion inhibitor.Yet, show that the blend of PCM and PAA has much lower corrosion rate, confirmed that PCM and PAA suppress the corrosive synergetic property.
1Annotate: the corrosion inhibition rate of the PAA that uses is not to be presented in the Table II separately, because thick scale deposition is arranged on sample tube and therefore to compare with all the other tests (the not sample tube of fouling) to be invalid.
Claims (12)
1, suppress fouling and/or corrosion compositions, it comprises: (a) poly aspartic acid and (b) have the water-soluble phosphate oligopolymer salt of following general formula:
H[CHRCHR]
n-PO
3M
2
Wherein, at least one R base is COOM in each unit, CH
2OH, sulfonic group or phosphono, and another R base can be identical or different with first R group, is hydrogen or COOM, hydroxyl, phosphono, sulfonic group, sulfate, C
1-7Alkyl, C
1-7Alkenyl or carboxylicesters, the C that phosphono, sulfonic group, sulfate and/or hydroxyl replace
1-7Alkyl or C
1-7Alkenyl, and each M be positively charged ion so that the phosphatization oligopolymer is water miscible, and n is 1-6, and
(b) it is 4: 1 to 1: 9 with (a) weight ratio.
2, composition as claimed in claim 1, n is greater than 1 and less than 6 in the wherein said general formula.
3, composition as claimed in claim 1, wherein water-soluble phosphoric acid salinization oligopolymer has following general formula:
H[CH(CO
2Na)-CH(CO
2Na)]
nPO
3Na
2
Wherein n is 1 to 5.
4, composition as claimed in claim 1, wherein poly aspartic acid is to be selected from poly aspartic acid, its salt, its derivative and their mixture.
5, composition as claimed in claim 1, wherein the molecular-weight average of poly aspartic acid is 500 to 10000 by gel permeation chromatography.
6, composition as claimed in claim 5, it comprises at least a annexing ingredient, this annexing ingredient is selected from vinylformic acid/sulfonic acid copolymer, vinylformic acid/maleic acid and their mixture.
7, composition as claimed in claim 6, wherein the weight ratio of phosphatization oligopolymer and poly aspartic acid is 1: 4 to 1: 9.
8, composition as claimed in claim 7, wherein the molecular-weight average of poly aspartic acid is 2000 to 4000 by gel permeation chromatography.
9, composition as claimed in claim 8, it comprises at least a annexing ingredient, this annexing ingredient is selected from tolyl-triazole, benzotriazole, orthophosphoric acid salt and polyphosphate.
10, a kind of each described composition that uses claim 1-9 suppresses the method for fouling in aqueous systems, it is characterized in that, described composition is added in the described aqueous systems, and wherein said composition is to use with the concentration of 5ppm to 200ppm.
11, method as claimed in claim 10, wherein said fouling is a lime carbonate.
12, a kind of each described composition of claim 1-9 that uses suppresses corroding method in aqueous systems, it is characterized in that, described composition is added in the described aqueous systems, and wherein said composition is to use with the concentration of 5ppm to 200ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/238,850 | 1999-01-28 | ||
| US09/238,850 US6207079B1 (en) | 1999-01-28 | 1999-01-28 | Scale and/or corrosion inhibiting composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1339015A CN1339015A (en) | 2002-03-06 |
| CN1166576C true CN1166576C (en) | 2004-09-15 |
Family
ID=22899585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008032459A Expired - Lifetime CN1166576C (en) | 1999-01-28 | 2000-01-26 | Scale and/or corrosion inhibiting composition |
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| Country | Link |
|---|---|
| US (2) | US6207079B1 (en) |
| EP (1) | EP1152986B1 (en) |
| JP (1) | JP4298927B2 (en) |
| KR (1) | KR100623541B1 (en) |
| CN (1) | CN1166576C (en) |
| AT (2) | ATE314318T1 (en) |
| AU (1) | AU756599B2 (en) |
| BE (1) | BE1013258A4 (en) |
| CA (1) | CA2297013C (en) |
| CH (1) | CH694764A5 (en) |
| DE (2) | DE60025164T2 (en) |
| DK (2) | DK1152986T3 (en) |
| ES (2) | ES2255975T3 (en) |
| FI (1) | FI20000155A (en) |
| FR (1) | FR2789069B1 (en) |
| GB (1) | GB2351076B (en) |
| HK (1) | HK1044751A1 (en) |
| IE (1) | IE20000067A1 (en) |
| IT (1) | IT1317738B1 (en) |
| LU (1) | LU90510B1 (en) |
| NL (1) | NL1014181C2 (en) |
| NO (1) | NO324664B1 (en) |
| NZ (1) | NZ513682A (en) |
| SE (1) | SE519742C2 (en) |
| TW (1) | TWI274071B (en) |
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| ZA (1) | ZA200000295B (en) |
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| US6403028B1 (en) * | 1999-10-18 | 2002-06-11 | Ashland Inc. | All-organic corrosion inhibitor composition and uses thereof |
| JP2002102886A (en) * | 2000-10-02 | 2002-04-09 | Sakai Chem Ind Co Ltd | Scale inhibitor and scale preventing method |
| US6503400B2 (en) | 2000-12-15 | 2003-01-07 | Ashland Inc. | Phosphate stabilizing compositions |
| DE10127004B4 (en) * | 2001-06-01 | 2005-08-18 | Clariant Gmbh | The use of electrochemically inhibited water / glycol mixtures as deicing and anti-icing agents |
| JP4859158B2 (en) * | 2001-06-29 | 2012-01-25 | 伯東株式会社 | Water treatment composition |
| US7078370B2 (en) * | 2001-09-19 | 2006-07-18 | Baker Hughes Incorporated | Biodegradable chelant compositions for fracturing fluid |
| US7048803B2 (en) * | 2003-01-29 | 2006-05-23 | Jones-Hamilton Co. | Method of dissolving scale |
| CN100509654C (en) * | 2004-08-31 | 2009-07-08 | 中国石化北京燕化石油化工股份有限公司 | Low-phosphorus composite antiincrustation corrosion inhibitor and use for water treatment |
| CN1328189C (en) * | 2005-07-14 | 2007-07-25 | 姚可佩 | Method for descaling steel-making turbid circulation water |
| KR100965563B1 (en) | 2009-12-30 | 2010-06-23 | 중앙크리텍 주식회사 | Eco-friendly organic/inorganic hybrid composition and an eco-friendly process of removing scale in concrete conduit by using the same |
| US8936728B2 (en) | 2010-08-31 | 2015-01-20 | Debra A. Riggs | Chemicals for oil spill cleanup |
| US9023779B2 (en) | 2013-03-15 | 2015-05-05 | Ecolab Usa Inc. | Inhibiting corrosion of aluminum on consumer ware washing product using phosphinosuccinic acid oligomers |
| US9290850B2 (en) * | 2013-10-31 | 2016-03-22 | U.S. Water Services Inc. | Corrosion inhibiting methods |
| CN104705315A (en) * | 2013-12-13 | 2015-06-17 | 东莞市天峻水处理机电工程有限公司 | Composite scale inhibition scale inhibiting, sterilizing and alga killing agent |
| WO2015134048A1 (en) | 2014-03-06 | 2015-09-11 | Solenis Technologies Cayman, L.P. | Composition and method of scale control in regulated evaporative systems |
| US9133418B1 (en) * | 2014-04-07 | 2015-09-15 | Ecolab Usa Inc. | Non-silicated high alkaline cleaner with aluminum protection |
| RU2580685C2 (en) * | 2014-07-04 | 2016-04-10 | Акционерное общество "Химический завод им. Л.Я. Карпова" | Corrosion and scaling inhibitor |
| CA2956455C (en) | 2014-08-08 | 2021-01-26 | Nch Corporation | Composition and method for treating white rust |
| EP3215468B1 (en) | 2014-11-04 | 2020-05-13 | Tennant Company | Liquid treatment systems and methods |
| US11104587B2 (en) | 2016-04-14 | 2021-08-31 | Nch Corporation | System and method for automated control, feed, delivery verification, and inventory management of corrosion and scale treatment products for water systems |
| US10351453B2 (en) * | 2016-04-14 | 2019-07-16 | Nch Corporation | Composition and method for inhibiting corrosion |
| US11085118B2 (en) * | 2016-04-14 | 2021-08-10 | Nch Corporation | Composition and method for inhibiting corrosion and scale |
| CN105645604A (en) * | 2016-04-22 | 2016-06-08 | 潘福昆 | Low-phosphorus scale and corrosion inhibitor |
| CN105858917A (en) * | 2016-05-27 | 2016-08-17 | 泗洪雅苏中草药种植有限公司 | Traditional Chinese medicine water scale removal piece, water purifying piece and preparation method thereof |
| CA3068248A1 (en) * | 2017-06-27 | 2019-01-03 | Nch Corporation | Composition and method for inhibiting corrosion and scale |
| US11525186B2 (en) | 2019-06-11 | 2022-12-13 | Ecolab Usa Inc. | Corrosion inhibitor formulation for geothermal reinjection well |
| CN112574720B (en) * | 2019-09-30 | 2021-12-07 | 中国石油化工股份有限公司 | Low-temperature heat transfer medium with function of inhibiting deposit formation and preparation method and application thereof |
| CN111377549A (en) * | 2020-03-13 | 2020-07-07 | 大唐绥化热电有限公司 | Special corrosion and scale inhibitor for recycling reclaimed water in power plant and preparation method thereof |
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| US5386038A (en) * | 1990-12-18 | 1995-01-31 | Albright & Wilson Limited | Water treatment agent |
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